EP3377489A1 - Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre - Google Patents

Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre

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Publication number
EP3377489A1
EP3377489A1 EP16790995.1A EP16790995A EP3377489A1 EP 3377489 A1 EP3377489 A1 EP 3377489A1 EP 16790995 A EP16790995 A EP 16790995A EP 3377489 A1 EP3377489 A1 EP 3377489A1
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EP
European Patent Office
Prior art keywords
alkyl
spp
group
cyano
mono
Prior art date
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EP16790995.1A
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German (de)
English (en)
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EP3377489B1 (fr
Inventor
Pierre Joseph Marcel Jung
Andrew Edmunds
Michel Muehlebach
André Jeanguenat
Daniel EMERY
Roger Graham Hall
Vikas SIKERVAR
Jagadish Pabba
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Syngenta Participations AG
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Syngenta Participations AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents

Definitions

  • the present invention relates to pesticidally active, in particular insecticidally active heterocyclic derivatives containing sulphur substituents, to processes for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.
  • Heterocyclic compounds with pesticidal action are known and described, for example, in
  • Y is O or S
  • R 2 is hydrogen, halogen, Ci-C 6 haloalkyl or Ci-C 6 alkyl; or
  • R 2 is Ci-C 6 haloalkylsulfanyl, Ci-C 6 haloalkylsulfinyl, Ci-C 6 haloalkylsulfonyl, Ci-C 6 alkylsulfanyl, d- C 6 alkylsulfinyl, Ci-C 6 alkylsulfonyl, d-C 6 alkoxy, Ci-C 6 haloalkoxy, Ci-C 4 haloalkoxyCi-C 4 alkyl, d- C 4 alkoxyCi-C 4 alkyl, SF 5 , cyano, C 3 -C 6 cycloalkylCi-C 4 alkyl or -C(0)Ci-C 6 haloalkyl; or
  • R 2 is C 3 -C 6 cycloalkyl, which can be mono- or polysubstituted by substituents selected from R 6 ;
  • R 4 is hydrogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, or is C 3 -C 6 cycloalkyl which can be mono- or poly- substituted by R 2 o; or is C 3 -C 6 cycloalkyl-Ci-C 4 alkyl which can be mono- or polysubstituted by R 20 ; or R 4 is Ci-C 4 alkyl substituted by R 7 ; or
  • R 4 is C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Ci-C 6 haloalkoxy, d-C 6 alkoxy, d-dalkoxy d-dalkyl , Ci-C 6 alkylsulfanyl, d-dalkylsulfonyl, d-C 6 alkylsulfinyl, d- dhaloalkylsulfanyl, d-C 6 haloalkylsulfonyl, d-C 6 haloalkylsulfinyl, amine or hydroxyl;
  • R 4 is d-C 6 alkenyl substituted by R 7 , or is d-C 6 alkynyl substituted by R 7 ;
  • R 5 is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl or d-dalkyl substituted by d-dalkylsulfanyl;
  • R 6 and R 20 are selected from the group consisting of cyano, halogen, d-C 6 alkyl and d-dhaloalkyl;
  • R 7 is cyano, halogen, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfonyl, d -C 4 al ky Is u If i ny I , d-C 4 alkoxy, d- C 4 alkoxyCi-C 4 alkoxy or phenyl which itself can be mono- or polysubstituted by substituents selected from R 8 ;
  • R 8 is halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl or Ci-C 4 alkoxy;
  • R 3 is a radical selected from the group consisting of formula Q-i , Q 2 , Q3, Q 4 , Q5, (3 ⁇ 4, Q7, (3 ⁇ 4, (3 ⁇ 4, Q10, Q-i -i , Q-12, Qi3 and Q 14;
  • A represents CH or N
  • X is S, SO or S0 2 ;
  • Ri is Ci-C 4 alkyl or Ci-C 4 haloalkyl
  • Ri is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • Ri is C 3 -C 6 cycloalkyl-Ci-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl;
  • R 9 is hydrogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, Ci-C 4 alkoxyCi-C 4 alkyl, hydroxyl, d-C 6 alkoxy or
  • R 9 is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 9 is C 3 -C 6 cycloalkyl-Ci-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 9 is C 3 -C 6 cycloalkylcarbonyl
  • R-io is hydrogen, Ci-C 6 alkyl, cyano, d-C 6 alkoxy, Ci-C 6 haloalkoxy, C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, amino, NH-CN, N-(Ci-C 4 alkyl)amino, N-(C C 4 alkyl)N-(C C 4 alkyl)amino, N-(C 3 -C 6 cycloalkyl)amino, N-(C C 4 alkyl)N-(C 3 -C 6 cycloalkyl)amino, N-(Ci-C 4 alkylcarbonyl)amino, N-(d-dalkyl)N-(d- C 4 alkylcarbonyl)amino, N-(Ci-C 4 alkyl)N-(C 3 -C 6 cycloalkylcarbonyl)amino, N-(C 3 -C 6 cycloal
  • heteroaromatic ring system can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen atoms and more than 2 sulfur atoms, said five- to six-membered ring system can be mono- or polysubstituted by substituents independently selected from the group V;
  • R-i-i is hydrogen, Ci-C 6 alkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, amino, N-d-C 4 alkylamino, N-(d-C 4 alkyl)N-(C 3 -d cycloalkyl)amino, N-(C 3 -dcycloalkyl)amino or N-(d-dalkyl) N-(d-C 4 alkyl)amino; or R-11 is d-dalkyl mono- or polysubstituted by substituents independently selected from the group Z; or R-11 is C 3 -dcycloalkyl which can be mono - or polysubstituted by substituents selected from the group consisting of halogen, d-dhaloalkyl, cyano and d-dalkyl; or
  • R-11 is C 3 -C 6 cycloalkyl-d-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, d-dhaloalkyl, cyano and d-dalkyl; or
  • R-11 is a five- to six-membered aromatic or heteroaromatic ring system, said aromatic or
  • heteroaromatic ring system can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen atoms and more than 2 sulfur atoms, said five- to six-membered aromatic or heteroaromatic ring system can be mono- or polysubstituted by substituents independently selected from the group V;
  • R-12 is hydrogen, Ci-C 6 alkyl, d-C 6 alkoxy, hydroxy or Ci-C 6 haloalkoxy; or
  • R-I2 is Ci-C 4 alkyl mono- or polysubstituted by substituents independently selected from the group Z; or R-I2 is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R-12 is C 3 -C 6 cycloalkyl-Ci-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl;
  • R-I3 is Ci-C 4 alkyl, Ci-C 4 haloalkyl, N-Ci-C 4 alkylamino, N,N-(Ci-C 4 alkyl) 2 amino or phenyl; said phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, d- C 4 alkyl, cyano, Ci-C 4 haloalkyl and Ci-C 4 alkoxy; or
  • R 13 is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 13 is C 3 -C 6 cycloalkylCi-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl;
  • R 21 is Ci-C 4 alkyl, Ci-C 4 haloalkyl, N-Ci-C 4 alkylamino, N,N-(Ci-C 4 alkyl) 2 amino or phenyl; said phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, d- C 4 alkyl, cyano, Ci-C 4 haloalkyl and Ci-C 4 alkoxy; or
  • R 2 i is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 2 i is C 3 -C 6 cycloalkylCi-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl;
  • n 0, 1 or 2;
  • 4 is hydrogen or Ci-C 6 alkyl;
  • R 15 is hydrogen, d-d alkyl, d-C 6 alkoxy, d-C 6 haloalkoxy, amino, N-d-dalkylamino or N,N-(d-C 4 alkyl) 2 amino; or
  • R-I5 is d-dalkyl mono- or polysubstituted by substituents independently selected from the group Z; or R 15 is C 3 -dcycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, d-dhaloalkyl, cyano and d-dalkyl; or
  • R 15 is C 3 -dcycloalkyl-d-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, d-dhaloalkyl, cyano and d-dalkyl;
  • p is 0 or 1 ;
  • R 16 is hydrogen or d-d alkyl
  • R-I7 is hydrogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy or d- haloalkoxy; or
  • R 17 is amino which can be mono- or disubstituted by substituents selected from the group consisting of cyano, d-dalkyl, d-dalkoxy, d-dhaloalkoxy, d-dcycloalkyl and d-dcycloalkyl-d-dalkyl, said C 3 -C 6 cycloalkyl and C 3 -C 6 cycloalkyl-Ci-C 4 alkyl groups itself can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or R-I7 is Ci-C 4 alkyl mono- or polysubstituted by substituents independently selected from Z; or
  • R-I7 is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 17 is C 3 -C 6 cycloalkyl-Ci-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 17 is a five- to six-membered ring aromatic or heteroaromatic ring system, said aromatic or heteroaromatic ring system can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, with the proviso that each ring system cannot contain more than 2 oxygen atoms and more than 2 sulfur atoms, said five- to six-membered aromatic or heteroaromatic ring system can be mono- to polysubstituted by substituents independently selected from V;
  • R 18 is hydrogen, halogen, amino, cyano, Ci-C 4 alkyl, C 3 -C 6 cycloalkyl, Ci-C 4 haloalkyl or C 3 -C 6 cycloalkyl substituted by cyano, Ci-C 3 haloalkyl, Ci-C 3 alkyl and halogen;
  • Rig is hydrogen, Ci-C 6 alkyl, d-C 6 alkoxy, Ci-C 6 haloalkoxy, C 3 -C 6 cycloalkylCi-C 4 alkyl, C 3 -C 6 cycloalkyl; Z is cyano, halogen, hydroxy, -SH, amino, nitro, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, Ci-C 4 alkylsulfanyl, d- C 4 haloalkylsulfanyl, Ci-C 4 alkylsulfinyl, Ci-C 4 haloalkylsulfinyl, Ci-C 4 alkylsulfonyl, Ci-C 4 haloalkylsulfonyl or phenyl; said phenyl can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 alkylsulfanyl, Ci-C 4
  • V is cyano, halogen, d-dalkyl, d-d cycloalkyl, d-dalkoxy, d-dalkoxyd-d alkyl, d-dhaloalkyl, d-dhaloalkoxy, d-dalkylsulfanyl, d-dhaloalkylsulfanyl, d-dalkylsulfinyl, d-dhaloalkylsulfinyl, d-dalkylsulfonyl or Ci-dhaloalkylsulfonyl; and agrochemically acceptable salts, stereoismers, enantiomers, tautomers and N-oxides of the compounds of formula I.
  • Compounds of formula I which have at least one basic centre can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrose acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as d-dalkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as d-C 4 alkane- or arylsulfonic acids which are unsubstituted or substituted, for
  • Compounds of formula I which have at least one acidic group can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.
  • bases for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethy
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, nonyl, decyl and their branched isomers.
  • Alkylsulfanyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned.
  • the alkenyl and alkynyl groups can be mono- or polyunsaturated.
  • Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.
  • Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1-difluoro-2,2,2-trichloroethyl, 2,2,3,3- tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,
  • Alkoxy groups preferably have a preferred chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy.
  • Alkoxyalkyl groups preferably have a chain length of 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkylsulfanyl is for example methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl,
  • Alkylsulfinyl is for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, a butylsulfinyl, pentylsulfinyl, and hexylsulfinyl.
  • Alkylsulfonyl is for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, pentylsulfonyl, and hexylsulfonyl.
  • the cycloalkyl groups preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Haloalkoxy groups preferably have a chain length of from 1 to 4 carbon atoms.
  • Haloalkoxy is, for example, difluoromethoxy, trifluoromethoxy or 2,2,2-trifluoroethoxy.
  • Haloalkylsulfanyl groups preferably have a chain length of from 1 to 4 carbon atoms.
  • Haloalkylsulfanyl is, for example, difluoromethylsulfanyl, trifluoromethylsulfanyl or 2,2,2-trifluoroethylsulfanyl. Similar considerations apply to the radicals Ci-C 4 haloalkylsulfinyl and Ci-C 4 haloalkylsulfonyl, which may be, for example, trifluoromethylsulfinyl, , trifluoromethylsulfonyl or 2,2,2-trifluoroethylsulfonyl.
  • mono- to polysubstituted in the definition of the substituents, means typically, depending on the chemical structure of the substituents, monosubstituted to seven-times substituted, preferably monosubstituted to five-times substituted, more preferably mono-, double- or triple-substituted.
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • a five- to six-membered aromatic or heteroaromatic ring system which can contain 1 to 4 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it not being possible for each ring system to contain more than 2 oxygen atoms and more than 2 sulfur atoms, are preferably selected from the group consisting of the following aromatic or heteroaromatic groups: phenyl, pyrrolyl; pyrazolyl; isoxazolyl; furanyl; thienyl; imidazolyl; oxazolyl; thiazolyl; isothiazolyl; triazolyl; oxadiazolyl; thiadiazolyl; tetrazolyl; furyl; pyridyl; pyrimidyl; pyrazinyl; pyridazinyl; triazinyl, pyranyl; (1 H-pyr
  • R 7 is cyano, Ci-C 4 alkylsulfanyl, Ci-C 4 alkylsulfonyl, C 1 -C 4 alkylsulfinyl, d-C 4 alkoxy, d- C 4 alkoxyCi-C 4 alkoxy or phenyl which itself can be mono- or polysubstituted by substituents selected from R 8 ;
  • R 9 is hydrogen, Ci-C 6 alkyl, Ci-C 6 haloalkyl, Ci-C 4 alkoxyCi-C 4 alkyl, hydroxyl or d-C 6 alkoxy; or
  • R 9 is C 3 -C 6 cycloalkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; or
  • R 9 is C 3 -C 6 cycloalkyl-Ci-C 4 alkyl which can be mono- or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl; and
  • R 18 is hydrogen, halogen, amino, cyano, Ci-C 4 alkyl or Ci-C 4 haloalkyl;
  • a preferred group of compounds of formula I is represented by the compounds of formula 1-1
  • R 3 is a radical selected from the group consisting of formulae Q-i , Q 2 , Q 3 , Q 4 , (3 ⁇ 4, (3 ⁇ 4, Q7, (3 ⁇ 4,
  • A, R 2 , R4, Rg, R10, Rn , R12, R14, R15, R16, R17, R18 and R 19 are as defined under formula I above;
  • X is S, SO or S0 2 ;
  • Ri is methyl, ethyl, n-propyl, i-propyl or cyclopropyl methyl, preferably ethyl; and
  • R 5 is as defined above under formula I, preferably methyl, and agrochemically acceptable salts, stereoismers, enantiomers, tautomers and N-oxides of those compounds.
  • R 5 is preferably methyl.
  • a further preferred embodiment of said preferred groups of compounds of formula 1-1 comprises compounds of formula I- 1 , wherein A is preferably N; X is preferably S or S0 2 and R-i is preferably ethyl.
  • R 3 is preferably selected from the group Q consisting of Q-i to Q 6
  • R 18 is hydrogen; A, R 9 , R 10 and R-n are as defined under formula I above; X is S, SO or S0 2 ; R-i is methyl, ethyl, n-propyl, i-propyl or cyclopropylmethyl, preferably ethyl; and R 5 is as defined above under formula I, preferably methyl, and agrochemically acceptable salts, stereoismers, enantiomers, tautomers and N-oxides of those compounds.
  • a further preferred embodiment of the invention comprises compounds of formula I represented by the compounds of formula 1-1
  • R 2 is Ci-C 4 haloalkyl, in particular trifluoromethyl
  • R 4 is C 1 -C4 alkyl or C 3 -C 6 cycloalkyl, in particular methyl, ethyl or cyclopropyl;
  • R 5 is C 1 -C4 alkyl, in particular methyl
  • R 3 is selected from the group consisting of Q-i to Q 6
  • Ri is C1-C4 alkyl, in particular ethyl
  • X is S, SO or S0 2 , in particular S or S0 2 ;
  • R 9 , R-io and R-n are as defined under formula I above;
  • R 18 is hydrogen
  • A is N or CH; and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N- oxides of the compounds of formula 1-1.
  • A is N or CH
  • R 2 is Ci-C 4 haloalkyl, in particular trifluoromethyl
  • X is S, SO or S0 2 , in particular S or S0 2 ;
  • R 3 is selected from the group consisting of Q-i to Q 6
  • R 18 is hydrogen; R-i is C1-C4 alkyl, in particular ethyl;
  • R 4 is C1-C4 alkyl or C 3 -C 6 cycloalkyl, in particular methyl, ethyl or cyclopropyl;
  • R 5 is C1-C4 alkyl, in particular methyl
  • R 9 is hydrogen or Ci-C 4 alkyl
  • R 9 is C 3 -C 6 cycloalkyl which can be mono - or polysubstituted by substituents selected from the group consisting of halogen, Ci-C 4 haloalkyl, cyano and Ci-C 4 alkyl;
  • R-io is hydrogen, Ci-C 6 alkyl, cyano, N-(d-C 4 alkyl)N-(C 3 -C 6 cycloalkylcarbonyl)amino,
  • R10 is Ci-C 4 alkyl mono- or disubstituted by a group selected from cyano and halogen; or
  • R-io is phenyl, pyridinyl or pyrazolyl; said phenyl, pyridinyl or pyrazolyl can be mono to polysubstituted by substituents independently selected from Ci-C 4 haloalkyl and halogen;
  • R11 is Ci-C 4 alkyl, N-Ci-C 4 alkylamino or N ,N-(Ci-C 4 alkyl) 2 amino;
  • A is N or CH
  • R 2 is Ci-C 4 haloalkyl, in particular trifluoromethyl
  • X is S, SO or S0 2 , in particular S or S0 2 ;
  • R 3 is selected from the group consisting of Q-i to Q 6
  • R 18 is hydrogen; R-i is C1-C4 alkyl, in particular ethyl;
  • R 4 is C1-C4 alkyl or C 3 -C 6 cycloalkyi, in particular methyl, ethyl or cyclopropyl;
  • R 5 is C1-C4 alkyl, in particular methyl
  • R 9 is hydrogen, Ci-C 4 alkyl or C 3 -C 6 cycloalkyl, in particular hydrogen, methyl or cyclopropyl;
  • R-io is hydrogen, Ci-C 6 alkyl; in particular hydrogen and methyl;
  • R11 is Ci-C 6 alkyl or C 3 -C 6 cycloalkyl, or Ci-C 6 alkyl or C 3 -C 6 cycloalkyl mono - or polysubstituted by substituents selected from the group consisting of hydrogen, halogen, Ci-C 4 haloalkyl, cyano and d- C 4 alkyl; in particular hydrogen, methyl and cyclopropyl.
  • Y is O
  • R 2 is C1-C2 haloalkyl
  • R 4 is Ci-C 3 alkyl or cyclopropyl
  • R 5 is C1-C3 alkyl
  • R 3 is selected from the group consisting of Q-i to Q 7 , Q g , Q 10 and Q-n
  • X is S, SO or S0 2 ; in particular S or S0 2 ;
  • Ri is C1-C3 alkyl
  • A is N or CH
  • R 9 is hydrogen, Ci-C 6 alkyl, C-rC 6 haloalkyl, hydroxyl or d-C 6 alkoxy; or
  • Rg is cyclopropylcarbonyl, cyclopropyl, cyclopropyl monosubstituted by cyano, or is S(0) 2 Ci-C 2 alkyl;
  • R-io is hydrogen, Ci-C 6 alkyl, S(0) 2 Ci-C 2 alkyl, S(0) 2 cyclopropyl, amino, N-(Ci-C 2 alkyl)amino or N-(Ci- C 2 alkyl)N-(cyclopropylcarbonyl)amino;
  • R10 is Ci-C 4 alkyl monosubstituted by cyano
  • Rn is Ci-C 6 alkoxy or cyclopropyl which can be substituted by cyano;
  • R 12 is hydroxyl or C1-C4 alkyl
  • R is C1-C4 alkyl
  • R is cyclopropyl
  • p 1 ;
  • R18 is hydrogen, C1-C3 alkyl, halogen, cyclopropyl or cyano and
  • R-ig is Ci-C 4 alkoxy.
  • WO 2013/191113, WO 2013/180193 and WO 2013/180194 comprises reaction of a compound of formula I I, wherein R 3 is selected from the group Q 1a to Q 14a
  • Z is X-R-i or a leaving group, for example a halogen
  • X, R-i , R 9 , R 10 , R- ⁇ , Ri 2 , R 13 , R 14 , R 15 , R 16 , R 17 , Ri8, R-I9 and A are as described under formula I above, and wherein the arrow in the radical Q shows the point of attachment to the carbon atom of the carboxyl group in the compound of formula II,
  • compounds lla where X 0 o is halogen, preferably chlorine, are formed by treatment of II with, for example, oxalyl chloride (COCI) 2 or thionyl chloride SOCI 2 in the presence of catalytic quantities of ⁇ , ⁇ -dimethylformamide DMF in inert solvents such as methylene chloride CH 2 CI 2 or tetrahydrofuran THF at temperatures between 20 to 100°C, preferably 25°C.
  • COCI oxalyl chloride
  • SOCI 2 thionyl chloride
  • Compounds of formula IV and/or IVa may further be converted into compounds of formula la, wherein R 3 is as defined above, and wherein R 2 , R 4 and R 5 are as described under formula I above, by dehydration, eg. by heating the compounds IV and/or IVa (or a mixture thereof) in the presence of an acid catalyst, such as for example methane sulfonic acid, or para-toluene sulfonic acid TsOH, in an inert solvent such as N-methyl pyrrolidine NMP at temperatures between 25-180°C, preferably 100-170°C, optionally under microwave conditions.
  • an acid catalyst such as for example methane sulfonic acid, or para-toluene sulfonic acid TsOH
  • an inert solvent such as N-methyl pyrrolidine NMP
  • hydrocarbons such as toluene and xylene, nitriles such as acetonitrile or polar aprotic solvents such as ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide.
  • nitriles such as acetonitrile or polar aprotic solvents
  • polar aprotic solvents such as ⁇ , ⁇ -dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone or dimethyl sulfoxide.
  • salts of the compound of formula V include compounds of the formula Va
  • this reaction can be carried out in the presence of a palladium catalyst, such as tris(dibenzylideneacetone)dipalladium(0), in the presence of a phosphor ligand, such as xanthphos, in an inert solvent, for example, xylene at temperatures between 100-160°C, preferably 140°C, as described by Perrio et al. in Tetrahedron 2005, 61 , 5253-5259.
  • a palladium catalyst such as tris(dibenzylideneacetone)dipalladium(0)
  • a phosphor ligand such as xanthphos
  • the subgroup of compounds of formula I, wherein X is SO (sulfoxide) and/or S0 2 (sulfone), may be obtained by means of an oxidation reaction of the corresponding sulfide compounds of formula I, wherein X is S (i.e. a compound of formula lb above), involving reagents such as, for example, m- chloroperoxybenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium
  • hypochlorite or tert-butyl hypochlorite amongst other oxidants are generally conducted in the presence of a solvent.
  • solvent to be used in the reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof.
  • Such oxidation reactions are disclosed, for example, in WO 2013/018928.
  • the sequence to prepare compounds of formula Ilia wherein R 2 , R4 and R 5 are as described under formula I above, from compounds of formula VIII, may involve i.
  • Y is an leaving group such as a halogen, for example a bromide or a amine protected or not, wherein R is hydrogen or a C1-C4 alkyl group and wherein R-i and R 18 are as defined in formula I above, may be prepared as described before for Qa analogues or R 3 analogues (see scheme 1 ,2 and 5). This transformation is illustrated by scheme 6.
  • Qb is selected from Qib to Q4
  • reaction can be catalyzed by a palladium based catalyst, for example Palladium acetate, in presence of a base, like cesium carbonate or sodium tert-butoxide, in a solvent or a solvent mixture, like, for example toluene, preferably under inert atmosphere and in presence of chelating phosphine such as BINAP or Xamtphos.
  • a palladium based catalyst for example Palladium acetate
  • a base like cesium carbonate or sodium tert-butoxide
  • solvent or a solvent mixture like, for example toluene
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture.
  • Similar reactions can be carried out in the presence of a copper source such as copper(l) iodide (Cul) or copper(ll) trifluoromethanesulfonate and a ligand such as 2,2'-bipyridine, proline, ⁇ , ⁇ '- dimethyl glycine or ethylene glycol, in the presence of a suitable base such as triethylamine, sodium carbonate, potassium carbonate, cesium carbonate, sodium methoxide, sodium tert- butoxide, potassium tert-but oxide.
  • a copper source such as copper(l) iodide (Cul) or copper(ll) trifluoromethanesulfonate
  • a ligand such as 2,2'-bipyridine, proline, ⁇ , ⁇ '- dimethyl glycine or ethylene glycol
  • the reaction can be carried out in a suitable solvent such as 1 ,4-dioxane, ⁇ , ⁇ -dimethylformamide, dimethyl sulfoxide or N-methylpyrolidinone at a temperature between 100 and 180 degrees centigrade for 15 to 60 minutes under microwave irradiation.
  • a suitable solvent such as 1 ,4-dioxane, ⁇ , ⁇ -dimethylformamide, dimethyl sulfoxide or N-methylpyrolidinone
  • compounds of formula I wherein R-i , R 2 , R4, R5 and X are as defined in formula I, can prepared by nucleophile substitution which involves for example, reaction of compounds of formula IXa, wherein Y is a leaving group, for example, fluorine with compounds of formula Xa under basic condition such as potassium carbonate in a solvent such as DMF, see for example Bioorganic & Medicinal Chemistry Letters 2013, 23(6), 1720-1726; WO 2010137349. See scheme 10.
  • compounds of formula IXb wherein X, R-i , R 2 , R4 and R 18 are as defined in formula I above can be prepared starting from compounds of formula IX wherein X, R-i , R 2 , R4 and R 18 are as defined in formula I above and wherein Y is a leaving group such as chloride or bromide, as shown in scheme 1 1 by substitution of a leaving group (LG) by a azide group coming, for example from sodium azide in a solvent such as A/,A/-Dimethylformamide or DMSO in presence or not of catalyst such as copper iodine in presence or a ligand such as proline or DMEDA, followed or not by reduction of the azide group in amine under classical reduction condition (see for example: Synthetic Organic
  • Alkylation may be achieved by treatment of the compounds of formula IX with R g -XLG 2 wherein XLG 2 is chloro, bromo, iodo, mesylate, triflate in presence of a base such as potassium carbonate in a solvent such as dimethylsulfoxide, acetonitrile, tetrahydrofuran, dimethylformamide or toluene could give compounds of formula I wherein X, R-i , R 2 , R 4 , R 5 , Rg, R 10 , R 18 and A are as defined in formula I above and wherein R 3 is selected from Q 5 and Q 6 wherein R 10 is hydrogen.
  • Such reactions can be carried out under well-established methods, described for example, Organic Preparations and Procedures International, 36(4), 347
  • XLG1 When XLG1 is OH such reactions are usually carried out in the presence of a coupling reagent, such as dicyclohexyl-carbo-diimide (“DCC”), N-(3- Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (“EDC”) or bis(2-oxo-3- oxazolidinyl)phosphonic chloride (“BOP-C1 "), in the presence of a base, and optionally in the presence of a nucleophilic catalyst, such as hydroxybenzo-triazole (“HOBT").
  • DCC dicyclohexyl-carbo-diimide
  • EDC N-(3- Dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride
  • BOP-C1 bis(2-oxo-3- oxazolidinyl)phosphonic chloride
  • HOBT hydroxybenzo-triazole
  • XLGi is CI
  • such reactions are usually carried out in the presence of a base, and optionally in the presence of a nucleophilic catalyst for example dimethylaminopyridine.
  • a nucleophilic catalyst for example dimethylaminopyridine.
  • XLGi is d-C 6 alkoxy it is sometimes possible to convert the ester directly to the amide by heating the ester and amine together in a thermal process.
  • Suitable bases include pyridine, triethylamine, 4-(dimethylamino)-pyridine ("DMAP") or diisopropylethylamine (Hunig's base).
  • Preferred solvents are NN-dimethylacetamide, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane, ethyl acetate and toluene.
  • the reaction is carried out at a temperature of from 0 degrees centigrade to 100 degrees centigrade, preferably from 15 degrees centigrade to 30 degrees centigrade, in particular at ambient temperature.
  • Transformation C Compounds of formula I wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I above and wherein R 7 is selected from Q 2 and Q 3 , can be made by amide coupling from compound of formula I wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I above and wherein R 7 is selected from (3 ⁇ 4 and Q 10 wherein R 12 is OH.
  • transformations are well known for people skilled in the art and are, for example by coupling reaction with an amine group (see for example: Synthetic Organic Methodology: Comprehensive Organic Transformations; A Guide to Functional Group Preparations, Larock, R. C. 1989 p 972-976) or for example via an acid halides such as acyl chloride (see for example: Synthetic Organic Methodology: Comprehensive Organic Transformations; Aa Guide to Functional Group Preparations, Larock, R. C. 1989 p. 963) and then reaction with a nucleophile such as, for example amino group substituted or not HNRgR 10 (see for example: Synthetic Organic Methodology: Comprehensive Organic Transformations, A Guide to Functional Group Preparations, Larock, R. C. 1989 p 979). See scheme 13, Transformation F.
  • Transformation B Compounds of formula I wherein X, R-i , R 2 , R 4 , R 5 , Rg, R 10 , R-is and A are as defined in formula I above and wherein R 7 is selected from Q g and Q 10 wherein R 12 is OH can be made by 1 ) reaction of compounds of formula IXc wherein X, R-i , R 2 , R 4 , R 5 , Rg, R 10 , R-is and A are as defined in formula I above and wherein Q b is selected from Q 1 b and Q 2b wherein Y is a leaving group such as bromide with source of cyanide, such as zinc cyanide under or not metal catalysis such as palladium catalyst (see for example : Med.
  • compounds of formula I wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I above and wherein R 7 is selected from Q 2 and Q 3 can be made from compounds of formula I wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I above and wherein R 7 is selected from (3 ⁇ 4 and Q 10 wherein R 12 is Ci-C 6 alkoxy by reaction with HNRgR 10 under various conditions as described in Synthetic Organic Methodology: Comprehensive Organic Transformations: A Guide to Functional Group Preparations, Larock, R. C. 1989 p 987. See scheme 13, Transformation G. Scheme 13
  • This transformation could be made in two steps, via the same type of diol intermediate by 1 ) transformation of compounds of formula IXd wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I above and wherein Qb' is selected from Q 1 b ' and Q 2b ' wherein Y-i is a group of formula XIV to compounds of formula IXd wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I above and wherein Qb' is selected from Q 1 b ' and Q 2b ' wherein Z-i is diol analogues XlVa followed by 2) oxidative scission of diols to Aldehydes or ketone.
  • step 1 see, for example : Curr. Org. Chem., 2004, 8, 1 159; Chem. Rev., 1980, 80, 187; Chem. Rev., 1994, 94, 2483.
  • step 2 see, for example : Organic Letters, 12(7), 1552-1555; 2010; Synlett, (5), 739-742; 2009; Chemistry Letters, (12), 1951-2; 1982; Science of Synthesis 2007, p17-24; Synthesis, (1 ), 64-5; 1989 and cited references.
  • Rc is C1-C4 Alkoxy
  • hydrolysis of the vinylester function will give compounds of formula I wherein X, R-i , R 2 , R 4 , R 5 , Rg, R 10 , R-is and A are as defined in formula I above and wherein R 7 is selected from Q g and Q 10 .
  • This transformation is well known in literature and could be exemplified by : Journal of Organic Chemistry, 55(10), 31 14-8; 1990.
  • Y b1 can be a boron-derived functional group, as for example B(OH) 2 or B(OR b2 ) 2 wherein R b2 can be a d-C 6 alkyl group or the two groups OR b2 can form together with the boron atom a five- or six-membered ring, as for example a pinacol boronic ester.
  • the reaction can be catalyzed by a palladium based catalyst, for example tetrakis(triphenylphosphine)-palladium(0), bis(triphenyl- phosphine) palladium(ll) dichloride or (1 ,1 'bis(diphenylphosphino)-ferrocene)dichloropalladium- dichloromethane (1 : 1 complex), in presence of a base, like sodium carbonate or cesium fluoride, in a solvent (such as 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane) or a solvent mixture, like, for example a mixture of 1 ,2-dimethoxyethane and water, or of dioxane and water, preferably under inert atmosphere.
  • a palladium based catalyst for example tetrakis(triphenylphosphine)-palladium(0), bis(triphenyl- phosphine) pal
  • the reaction temperature can preferentially range from ambient temperature to the boiling point of the reaction mixture, or alternatively heating may be performed under microwave irradiation.
  • This reaction is known as Suzuki cross-coupling.
  • Suzuki reactions are well known to those skilled in the art and have been reviewed, for example J.Orgmet. Chem. 576, 1999, 147-168 or , Kurti, Laszlo; Czako, Barbara; (Editors) Strategic Applications of Named Reactions in Organic Synthesis (2005) p448.
  • compounds of formula IXd wherein X, R-i , R 2 , R 4 , R 5 , Rg, R 10 , R-is and A are as defined in formula I above and wherein Qb' is selected from Q 1 b ' and Q 2b ' wherein Y-i is a group of formula XIV can be prepared by a Stille reaction of compounds of formula Yb 2 -Y-i derivative wherein Y b2 is a trialkyl tin derivative, preferably tri-n-butyl tin, with compounds of formula IX wherein X, R-i , R 2 , R 4 , R 5 , Rg, R 10 , R and A are as defined in formula I above and wherein Qb is selected from Q 1 b and Q wherein Y is leaving group, for example, chlorine, bromine or iodine (preferably bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonate.
  • the subgroup of compounds of t ) defined as the sulfilimine I, wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I, may be prepared by reacting compounds of the compounds of formula IXb wherein X, R-i , R 2 , R4, R5, Rg, R10, R18 and A are as defined in formula I and where in Q c is selected from Q 1c and Q 2c , under imination reaction conditions (step A, Scheme 16).
  • Oxidants such as N-iodosuccinimide (NIS) or iodine may be also used alternatively as described, for example, in O.G. Mancheno, C. Bolm, Org. Lett. 2007, 9, 3809-381 1.
  • Typical preparation methods and reaction conditions to access the sulfoximines I (step B) from compounds of formula I (sulfilimines I), wherein X, R-i , R 2 , R 4 , R5, Rg, R10, R18 and A are classical oxidation reagents such as KMn0 4 , mCPBA, Nal0 4 /Ru0 2 , H 2 0 2 , oxone.
  • X, R-i , R 2 , R 4 , R5, Rg, R10, R18 and A are classical oxidation reagents such as KMn0 4 , mCPBA, Nal0 4 /Ru0 2 , H 2 0 2 , oxone.
  • Such reactions can be carried out under well-established methods, described for example, in Journal of Organic Chemistry 1979, p2510; Monatshefte fuer Chemie 1985, 1 16(10), 1 153-64.
  • compounds of formula I wherein R 3 is Qn or Q 12 wherein p is 1 can be prepared (scheme 16b) by reacting compounds of formula 1-1 , wherein R 3 is Q 1 b or Q 2b wherein Z is halogen such as bromide via a palladium coupling .
  • Such reactions are usually carried out in the presence of a palladium catalyst, for example fefra/c/ ' s(triphenylphosphine)palladium(0) or (1 E,4E)-1 ,5-diphenylpenta- 1 ,4-dien-3-one; palladium, in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive ligand, such as rac-BlNAP or 5-diphenylphosphanyl-9,9-dimethyl-xanthen-4- yl)-diphenyl-phosphane, and optionally in the presence of a base such as cesium carbonate.
  • a palladium catalyst for example fefra/c/ ' s(triphenylphosphine)palladium(0) or (1 E,4E)-1 ,5-diphenylpenta- 1 ,4-dien-3-one
  • Compounds of formula I, wherein Y is S can be prepared (scheme 17) by reacting compounds of formula 1-1 , wherein Y is O with a reagent that could transfer a sulphur atom such as, for example, the Lawesson's reagent in a solvent such as, for example dimethylformamide or toluene, usually at temperature between 50 to 150°C.
  • a reagent that could transfer a sulphur atom such as, for example, the Lawesson's reagent in a solvent such as, for example dimethylformamide or toluene, usually at temperature between 50 to 150°C.
  • This type of transformation is known to a person skilled in the art and are, for example, described in Tetrahedron (2007), 63(48), 1 1862-1 1877 or US20120309796.
  • the O of the C(O) can be transformed on S on previews intermediate such as for example , compounds of formula IX, IXc or IXd.
  • the reactants can be reacted in the presence of a base.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • sodium hydroxide sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert- butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine,
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, bases which are employed in excess, such as triethylamine, pyridine, N-methylmorpholine or ⁇ , ⁇ -diethylaniline, may also act as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately -80°C to approximately +140°C, preferably from approximately -30°C to approximately +100°C, in many cases in the range between ambient temperature and approximately +80°C.
  • a compound of formula I can be converted in a manner known per se into another compound of formula I by replacing one or more substituents of the starting compound of formula I in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula I can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula I can be converted in a manner known per se into other salts of compounds of formula I, acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula I which have salt- forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule; the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.
  • Diastereomer mixtures or racemate mixtures of compounds of formula I, in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diasteromers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.
  • Enantiomer mixtures such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid
  • N-oxides can be prepared by reacting a compound of the formula I with a suitable oxidizing agent, for example the H 2 0 2 /urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride.
  • a suitable oxidizing agent for example the H 2 0 2 /urea adduct
  • an acid anhydride e.g. trifluoroacetic anhydride
  • the compounds of formula I and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the compounds according to the following Tables 1 to 10 below can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula I.
  • Table 1 This table discloses the 10 compounds 1 .001 to 1.010 of the formula l-1a:
  • C 3 H 5 is cyclopropyl.
  • Table 2 This table discloses the 10 compounds 2.001 to 2.010 of the formula l-1a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i , Rn and A are as defined in Table 1.
  • Table 3 This table discloses the 10 compounds 3.001 to 3.010 of the formula l-1a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i , Rn and A are as defined in Table 1.
  • Table 4 This table discloses the 10 compounds 4.001 to 4.010 of the formula l-2a:
  • C 3 H 5 is cyclopropyl.
  • Table 5 This table discloses the 10 compounds 5.001 to 5.010 of the formula l-2a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i , Rn and A are as defined in Table 4.
  • Table 6 This table discloses the 10 compounds 6.001 to 6.019 of the formula l-2a, wherein X is S0 2 and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i , Rn and A are as defined in Table 4.
  • Table 7 This table discloses the 10 compounds 7.001 to 7.012 of the formula l-3a:
  • C 3 H 5 is cyclopropyl.
  • Table 8 This table discloses the 12 compounds 8.001 to 8.012 of the formula l-3a, wherein X is and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i , R 10 and A are as defined in Table 7.
  • Table 9 This table discloses the 12 compounds 9.001 to 9.012 of the formula l-3a, wherein X is and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i , R 10 and A are as defined in Table 7.
  • Table 10 This table discloses the 12 compounds 10.001 to 10.012 of the formula l-4a:
  • C 3 H 5 is cyclopropyl.
  • Table 11 discloses the 12 compounds 11.001 to 11.012 of the formula l-4a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i, Rn and A are as defined in Table 10.
  • Table 12 This table discloses the 12 compounds 12.001 to 12.012 of the formula l-4a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i, R- ⁇ and A are as defined in Table 10.
  • Table 13 This table discloses the 10 compounds 13.001 to 13.010 of the formula l-5a:
  • Table 14 This table discloses the 10 compounds 14.001 to 14.010 of the formula l-5a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 12 and A are as defined in Table 13.
  • Table 15 This table discloses the 10 compounds 15.001 to 15.010 of the formula l-5a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 12 and A are as defined in Table 13.
  • Table 16 This table discloses the 10 compounds 16.001 to 16.010 of the formula l-6a:
  • Table 17 This table discloses the 10 compounds 17.001 to 17.010 of the formula l-6a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i, R 12 and A are as defined in Table 16.
  • Table 18 This table discloses the 10 compounds 18.001 to 18.010 of the formula l-6a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i, R 12 and A are as defined in Table 16.
  • Table 19 This table discloses the 12 compounds 19.001 to 19.012 of the formula l-7a:
  • Table 20 This table discloses the 12 compounds 20.001 to 20.012 of the formula l-7a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i, R 10 and A are as defined in Table 19.
  • Table 21 This table discloses the 12 compounds 21.001 to 21.012 of the formula l-7a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-i, R 10 and A are as defined in Table 19.
  • Table 22 This table discloses the 12 compounds 22.001 to 22.012 of the formula l-8a:
  • Table 23 This table discloses the 12 compounds 23.001 to 23.012 of the formula l-8a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-,, R 10 and A are as defined in Table 22.
  • Table 24 This table discloses the 12 compounds 24.001 to 24.012 of the formula l-8a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R 9 , R-,, R 10 and A are as defined in Table 22.
  • Table 25 This table discloses the 12 compounds 25.001 to 25.012 of the formula l-9a:
  • R 4 is CH 3
  • R 5 is CH 3
  • R 2 is CF 3
  • R-i R 16 , R 17 and A are as defined below:
  • C 3 H 5 is cyclopropyl.
  • Table 26 This table discloses the 12 compounds 26.001 to 26.012 of the formula l-9a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 16 , R 17 and A are as defined in Table 25.
  • Table 27 This table discloses the 12 compounds 27.001 to 27.012 of the formula l-9a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 16 , R 17 and A are as defined in Table 25.
  • Table 28 This table discloses the 12 compounds 28.001 to 28.012 of the formula l-10a:
  • C 3 H 5 is cyclopropyl.
  • Table 29 This table discloses the 12 compounds 29.001 to 29.012 of the formula l-10a, wherein X SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i, R 16 , R 17 and A are as defined in Table 28.
  • Table 30 This table discloses the 12 compounds 30.001 to 30.012 of the formula l-10a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 16 , R 17 and A are as defined in Table 28.
  • Table 31 This table discloses the 8 compounds 31.001 to 31.008of the formula 1-11a:
  • C 3 H 5 is cyclopropyl.
  • Table 32 This table discloses the 8 compounds 32.001 to 32.008 of the formula 1-11a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and p, R-i , R 14 , R 15 and A are as defined in Table 31.
  • Table 33 This table discloses the 8 compounds 33.001 to 33.008 of the formula 1-11a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and p, R-i , R 14 , R 15 and A are as defined in Table 31.
  • Table 34 This table discloses the 8 compounds 34.001 to 34.008 of the formula l-12a:
  • C 3 H 5 is cyclopropyl.
  • Table 35 This table discloses the 8 compounds 35.001 to 35.008 of the formula l-12a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and p, R-i , R 14 , R 15 and A are as defined in Table 34.
  • Table 36 This table discloses the 8 compounds 36.001 to 36.008 of the formula l-12a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and p, R-i , R 14 , R 15 and A are as defined in Table 34.
  • Table 37 This table discloses the 6 compounds 37.001 to 37.006 of the formula 1-13a: wherein X is S, R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i, R 9 , R 19 and A are as defined below: Table 37:
  • Table 38 discloses the 6 compounds 38.001 to 38.006 of the formula 1-13a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i, R 9 , R 19 and A are as defined in Table 37.
  • Table 39 discloses the 6 compounds 39.001 to 39.006 of the formula 1-13a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i, R 9 , R 19 and A are as defined in Table 37.
  • Table 40 This table discloses the 6 compounds 40.001 to 40.006 of the formula l-14a: wherein X is S, R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 9 , R 19 and A are as defined below: Table 40:
  • Table 41 discloses the 6 compounds 41.001 to 41.006 of the formula l-14a, wherein X is SO, and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 9 , R 19 and A are as defined in Table 40.
  • Table 42 This table discloses the 6 compounds 42.001 to 42.006 of the formula l-14a, wherein X is S0 2 , and R 4 is CH 3 , R 5 is CH 3 , R 2 is CF 3 and R-i , R 9 , R 19 and A are as defined in Table 40.
  • the compounds of formula I according to the invention are preventively and/or curatively valuable ac- tive ingredients in the field of pest control, even at low rates of application, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants.
  • the active ingredients according to the invention act against all or individual developmental stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i. e.
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
  • Agriotes spp. Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp, Astylus atromaculatus, Ataenius spp, Atomaria linearis, Chaetocnema tibialis, Cerotoma spp, Conoderus spp, Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp, Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemLineata, Lissorhoptrus spp., Liogenys spp, Maecolaspis spp, Maladera castanea, Megas
  • Acyrthosium pisum Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp, Brachycaudus spp, Brevicoryne brassicae, Cacopsylla spp, Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp, Cofana spec
  • Coptotermes spp Corniternes cumulans, Incisitermes spp, Macrotermes spp, Mastotermes spp, Microtermes spp, Reticulitermes spp.; Solenopsis geminate
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp. , Scapteriscus spp, and Schistocerca spp.;
  • Thysanoptera for example
  • Thysanura for example, Lepisma saccharina.
  • the active ingredients according to the invention can be used for controlling, i. e. containing or destroying, pests of the abovementioned type which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soya; oil crops, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • the invention may be used on any of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., Brassica spp.
  • Ageratum spp. Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp.
  • Coreopsis spp. Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp., Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (/.
  • Iresines spp. Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp., Nemesia spp., Tagetes spp., Dianthus spp. (carnation), Canna spp., Oxalis spp., Be//; ' s spp., Pelargonium spp. CP. peltatum, P. Zonale), Viola spp.
  • the invention may be used on any of the following vegetable species: Allium spp. (A sativum, A., cepa, A. oschaninii, A. Porrum, A. ascalonicum, A.
  • Daucus carota Foeniculum vulgare, Hypericum spp., Lactuca sativa, Lycopersicon spp. (L esculentum, L. lycopersicum), Mentha spp., Ocimum basilicum, Petroselinum crispum, Phaseolus spp. (P. vulgaris, P. coccineus), Pisum sativum, Raphanus sativus, Rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, Solanum melongena, Spinacea oleracea, Valerianella spp. (V. locusta, V.
  • Preferred ornamental species include African violet, Begonia, Dahlia, Gerbera, Hydrangea, Verbena, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hortensia, rosemary, sage, St. Johnswort, mint, sweet pepper, tomato and cucumber.
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the active ingredients according to the invention are especially suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, maize, rice and soya crops.
  • the active ingredients according to the invention are further especially suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apples), Empoasca(preferably in vegetables, vineyards), Leptinotarsa (preferably in potatos) and Chilo supressalis (preferably in rice).
  • the invention may also relate to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic-, Semiendoparasitic- and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolai
  • the compounds of the invention may also have activity against the molluscs.
  • Examples of which include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. Nemoralis); ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H.
  • H. aperta Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popilliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab,
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • amino acid replacements preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • the processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic crops are:
  • Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G- protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810. 4.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.
  • NK603 * MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 * MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • crops is to be understood as including also crop plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called
  • compositions according to the invention are the protection of stored goods and store ambients and the protection of raw materials, such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, especially the protection of humans, domestic animals and productive livestock against pests of the mentioned type.
  • the present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http://www.who.int/malaria/vector_control/irs/en/).
  • the method for controlling pests comprises applying the compositions of the invention to the target pests, to their locus or to a surface or substrate by brushing, rolling, spraying, spreading or dipping.
  • an IRS (indoor residual spraying) application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention.
  • the method for controlling such pests comprises applying a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • a pesticidally effective amount of the compositions of the invention to the target pests, to their locus, or to a surface or substrate so as to provide effective residual pesticidal activity on the surface or substrate.
  • Such application may be made by brushing, rolling, spraying, spreading or dipping the pesticidal composition of the invention.
  • an IRS application of a surface such as a wall, ceiling or floor surface is contemplated by the method of the invention so as to provide effective residual pesticidal activity on the surface.
  • it is contemplated to apply such compositions for residual control of pests on a substrate such as a fabric material in the form of (or which can be used in the manufacture of) netting, clothing, bedding, curtains and tents.
  • Substrates including non-woven, fabrics or netting to be treated may be made of natural fibres such as cotton, raffia, jute, flax, sisal, hessian, or wool, or synthetic fibres such as polyamide, polyester, polypropylene, polyacrylonitrile or the like.
  • the polyesters are particularly suitable.
  • the methods of textile treatment are known, e.g. WO 2008/151984, WO 2003/034823, US 5631072, WO 2005/64072, WO2006/128870, EP 1724392, WO2005/1 13886 or WO 2007/090739.
  • compositions according to the invention are the field of tree injection/trunk treatment for all ornamental trees as well all sort of fruit and nut trees.
  • the compounds according to the present invention are especially suitable against wood-boring insects from the order Lepidoptera as mentioned above and from the order Coleoptera, especially against woodborers listed in the following tables A and B:
  • Agrilus sayi Bayberry, Sweetfern
  • Rhododendron Rhadodendron, Azalea, Laurel, Poplar, Willow, Mulberry
  • Phloeotribus liminaris Peach, Cherry, Plum, Black cherry,
  • the present invention may be also used to control any insect pests that may be present in turfgrass, including for example beetles, caterpillars, fire ants, ground pearls, millipedes, sow bugs, mites, mole crickets, scales, mealybugs ticks, spittlebugs, southern chinch bugs and white grubs.
  • the present invention may be used to control insect pests at various stages of their life cycle, including eggs, larvae, nymphs and adults.
  • the present invention may be used to control insect pests that feed on the roots of turfgrass including white grubs (such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. Green June beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May/June beetle), Ataenius spp. (e.g. Black turfgrass ataenius, A.
  • white grubs such as Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp
  • Maladera spp. e.g. Asiatic garden beetle, M. castanea
  • Tomarus spp. ground pearls
  • mole crickets tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula spp.).
  • the present invention may also be used to control insect pests of turfgrass that are thatch dwelling, including armyworms (such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta), cutworms, billbugs (Sphenophorus spp. , such as S. venatus verstitus and S. parvulus), and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).
  • armyworms such as fall armyworm Spodoptera frugiperda, and common armyworm Pseudaletia unipuncta
  • cutworms such as S. venatus verstitus and S. parvulus
  • sod webworms such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis.
  • the present invention may also be used to control insect pests of turfgrass that live above the ground and feed on the turfgrass leaves, including chinch bugs (such as southern chinch bugs, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae family), and greenbugs.
  • the present invention may also be used to control other pests of turfgrass such as red imported fire ants (Solenopsis invicta) that create ant mounds in turf.
  • compositions according to the invention are active against ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • ectoparasites such as hard ticks, soft ticks, mange mites, harvest mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas. Examples of such parasites are:
  • Anoplurida Haematopinus spp., Linognathus spp., Pediculus spp. and Phtirus spp., Solenopotes spp..
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Calliphora spp., Glossina spp., Call
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergatesspp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,
  • Pterolichus spp. Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp..
  • compositions according to the invention are also suitable for protecting against insect infestation in the case of materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and buildings.
  • compositions according to the invention can be used, for example, against the following pests: beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec.,Tryptodendron spec, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec, and Dinoderus minutus, and also hymenopterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus
  • the compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • Such formulations can either be used directly or diluted prior to use.
  • the dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules.
  • Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release).
  • Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art.
  • very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4- dioxane, di
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.
  • a large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface- active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol est
  • Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.
  • compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • the amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied.
  • the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • Preferred oil additives comprise alkyl esters of C 8 -C 2 2 fatty acids, especially the methyl derivatives of Ci 2 -Ci 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively).
  • Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.
  • inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.
  • Preferred formulations can have the following compositions (weight %): Emulsifiable concentrates:
  • active ingredient 1 to 95 %, preferably 60 to 90 %
  • surface-active agent 1 to 30 %, preferably 5 to 20 %
  • liquid carrier 1 to 80 %, preferably 1 to 35 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 95 %, preferably 15 to 90 %
  • Granules 5 to 95 %, preferably 15 to 90 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.
  • the combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.
  • Emulsifiable concentrate I I active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene 3 %
  • Emulsions of any required dilution which can be used in plant protection, can be obtained from this concentrate by dilution with water.
  • Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.
  • the combination is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Active ingredients 8 % polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.
  • Non-dusty coated granules are obtained in this manner.
  • the finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %
  • Silicone oil (in the form of a 75 % emulsion in water) 0.2 %
  • 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ).
  • This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved.
  • a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added.
  • the mixture is agitated until the polymerization reaction is completed.
  • the obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent.
  • the capsule suspension formulation contains 28% of the active ingredients.
  • the medium capsule diameter is 8-15 microns.
  • the resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.
  • Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agricultural
  • Mp melting point in °C. Free radicals represent methyl groups. H NMR measurements were recorded on a Brucker 400MHz spectrometer, chemical shifts are given in ppm relevant to a TMS standard. Spectra measured in deuterated solvents as indicated.
  • aq aqueous
  • min minute
  • h hour
  • sat saturated
  • RT retention time
  • mCPBA meta- chloroperoxybenzoic acid
  • MeOH methanol
  • EtOH ethanol
  • NaHC0 3 sodium hydrogen carbonate
  • Na 2 C0 3 sodium carbonate
  • HCI hydrogen chloride
  • CH 2 CI 2 dichloromethane
  • Et 3 N triethylamine
  • DMF ⁇ , ⁇ -dimethylformamide
  • Solvent degasser binary pump, heated column compartment and diode-array detector.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector.
  • Spectra were recorded on a Mass Spectrometer from Waters (SQD or ZQ Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.00 kV, Cone range: 30-60 V, Extractor: 2.00 V, Source Temperature: 150°C, Desolvation Temperature: 350°C, Cone Gas Flow: 0 L/Hr, Desolvation Gas Flow: 650 L/Hr, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment and diode-array detector. Solvent degasser, binary pump, heated column compartment and diode-array detector.
  • Step A 1-ethyl-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one:
  • Step A Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid:
  • Step B Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid:
  • Step A Preparation of 5-bromo-N-[1-ethyl-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4-pyridyl]-3- ethylsulfanyl-pyridine-2-carboxamide and N-[4-amino-1-ethyl-2-oxo-6-(trifluoromethyl)-3-pyridyl]-5- bromo-3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide:
  • Example 11 2.00 g, 9.04 mmol) in ethyl acetate (100 ml) was added N,N-diethylethanamine (2.31 g, 3.18 mL, 22.6 mmol) then the resulting solution was cooled with an ice bath, before slow addition of the previous acid chloride solution. The resulting mixture was stirred 1 hour at 0°C. The solution was neutralized by addition of a saturated aqueous solution of sodium bicarbonate and the product was extracted twice with ethyl acetate. The organic solution was dried over sodium sulfate and evaporated under reduced pressure to yield the crude product.
  • Step B Preparation of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-ethyl-3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one:
  • Step C Preparation of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-5-ethyl-3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one:
  • Step A 1-methvl-3-(methvlamino)-6-(trifluoromethvl)pyridin-2-one:
  • Step C 4-amino-1-methyl-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one:
  • Step A methyl 3 , 6-d ich loropyrid ine-2-carboxylate
  • Step B Preparation of methyl 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylate:
  • the reaction mixture was poured on 100 ml saturated ammonium chloride aqueous solution, extracted with 2x 100ml Ethyl acetate, and the combined organic layers washed with 2x 50 ml saturated aqueous ammonium chloride aqueous solution, 3x 100 ml water, dried over Sodium sulfate, filtered and concentrated in vacuum.
  • the crude product was purified by combi flash chromatography with a column of 220 g and a gradient cyclohexane + 0-10% Ethyl acetate.
  • Step C 6-chloro-3-ethvlsulfanvl-pvridine-2-carboxylic acid
  • Example I6 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5- clpyridin-4-one:
  • Step A 6-chloro-3-ethylsulfanyl-N-[1-methyl-3-(methylamino)-2-oxo-6-(trifluoromethyl)-4- pyridyl]pyridine-2-carboxamide and N-[4-amino-1-methyl-2-oxo-6-(trifluoronriethyl)-3-pyridyl]-6-chloro- 3-ethylsulfanyl-N-methyl-pyridine-2-carboxamide:
  • Step B 2-(6-chloro-3-ethylsulfanyl-2-pyridyl)-3,5-dimethyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-4- one:
  • Example I7 2-(6-chloro-3-ethylsulfonyl-2-pyridvn-5-ethyl-3-methyl-6-(trifluoromethvnimidazo[4,5- clpyridin-4-one:
  • Step A 1-ethyl-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one:
  • Step B 1-ethyl-3-(methylamino)-4-nitro-6-(trifluoromethyl)pyridin-2-one:
  • Step C 4-amino-1-ethyl-3-(methylamino -6-(trifluoromethyl)pyridin-2-one:
  • 6-chloro-3-ethylsulfanyl-pyridine-2-carboxylic acid (as prepared in Example I5) (4.2 g, 19 mmol) was dissolved in dichloromethane (39 mL) with oxalyl dichloride (5.0 g, 39 mmol) and N,N- dimethylformamide (1 drop). The mixture was stirred for 30 min at room temperature then at reflux for 30 min.
  • 6-chloro-3-ethylsulfanyl-pyridine-2- carbonyl chloride (4.2 g, 18 mmol) was diluted with 5 ml of tetrahydrofuran and a solution of 4-amino- 1-ethyl-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one (4.6 g, 20 mmol) in tetrahydrofuran (36 mL) and pyridine (4.2 g, 4.3 mL) was added.
  • Step E 2-(6-chloro-3-ethylsulfanyl-2-pyridyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin- 4-one.
  • Step F 2-(6-chloro-3-ethylsulfonyl-2-pyridyl)-5-ethyl-3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin- 4-one.
  • Step A 1- cyclopropyl -3-(amino)-6-(trifluoromethyl)pyridin-2-one
  • N-[1-cyclopropyl- 2-hydroxy-6-oxo-2-(trifluoromethyl)-3H-pyridin-5-yl]benzamide was dissolved in hydrogen chloride (563 g, 473.1 mL, 5710 mmol) and the mixture was stirred at 100°C for Over Night.
  • the precipitate of Benzoic acid was filtered off and the filtrate was basified to pH 7-8 with a solution of sodium hydroxyl cone. Then the water phase was extracted (3x) with AcOEt and the combined organic layers were dried over sodium sulfate, filtered and concentrated under vacuum.
  • Step C 1- cyclopropyl -3-(methylamino)-4-nitro-6-(trifluoromethyl)pyridin-2-one
  • Step D 4-amino-1- cyclopropyl -3-(methylamino)-6-(trifluoromethyl)pyridin-2-one
  • the 4-amino-1- cyclopropyl-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one was prepared as for Example I2, step D.
  • LC-MS(Method A) RT 0.52, 247 (M + H + ).
  • the 4-amino-1- cyclopropyl-3-(methylamino)-6-(trifluoromethyl)pyridin-2-one could be prepared via hydrogenation in presence of Pd/C in ethanol using classical reaction.
  • Example P3 Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2-yll-5- ethylsulfonyl-pyridine-3-carboxylic acid A3.
  • Step A Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- ethylsulfonyl-pyridine-3-carbonitrile
  • Step B Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- ethylsulfonyl-pyridine-3-carboxylic acid A3.
  • Example P4 Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2-yll-5- ethylsulfonyl-pyridine-2-carboxylic acid A4.
  • Step A Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridii ethylsulfonyl-pyridine-2-carbonitrile
  • Step B Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridii
  • Example P5 Preparation of 2-(5-amino-3-ethylsulfonyl-2-pyridyl)-5-ethyl-3-methyl-6- (trifluoromethyl)imidazo[4,5-clpyridin-4-one A5.
  • Step B 2-(5-amino-3-ethvlsulfonvl-2-pvridvl)-5-ethvl-3-methvl-6-(trifluoromethyl)imidazo[4,5-clpvridin- 4-one.
  • Example P6 Preparation of 2-(6-amino-3-ethylsulfonyl-2-pyridvD-5-ethyl-3-methyl-6- (trifluoromethvDimidazo[4,5-clpyridin-4-one A6.
  • reaction was purged with nitrogen for 10 mins followed by addition of Palladium (II) acetate (237 mg, 1.00 mmol) and then heated at 1 10°C for overnight.
  • the reaction was diluted with water (150 ml), extracted with ethyl acetate. The combined organic layers were washed successively with water and brine, dried over Sodium sulfate and concentrated in vacuo.
  • Step B 2-(6-amino-3-ethvlsulfonvl-2-pvridvl)-5-ethvl-3-methvl-6-(trifluoromethyl)imidazo[4,5-clpvridin- 4-one.
  • cyclopropane carbonyl chloride (0.8384 mmol, 0.08764 g) was added dropwise under ice bath and stirred for 6 Hours at room temperature, and the reaction mixture was then quenched by adding 10ml of water and 15 ml of dichloromethane. Organic and aqueous layer were separated in separating funnel, aqueous layer re-extracted with dichloromethane (2X15 mL). Combined org layer was washed with brine and concentrated under reduced pressure.
  • Example P9 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2-yll- 5-ethylsulfonyl-3-pyridyll-N-methyl-cyclopropanecarboxamide A9.
  • Step A tert-butyl N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridii ethylsulfonyl-3-pyridyl]carbamate A64
  • Step B tert-butyl N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridii
  • Step C 5-ethyl-2-[3-ethylsulfonyl-5-(methylamino)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-4-one.
  • Step D N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3- pyridyl]-N-methyl-cyclopropanecarboxamide A9.
  • Example P10 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-2-pyridyll-N-methyl-cyclopropanecarboxamide A10.
  • Step A tert-butyl N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridii
  • reaction was purged with nitrogen for 10 mins followed by addition of Palladium (II) acetate (237 mg, 1.00 mmol) and then heated at 1 10°C for overnight.
  • the reaction was diluted with water (150 ml), extracted with ethyl acetate. The combined organic layers were washed successively with water and brine, dried over Sodium sulfate and concentrated in vacuo.
  • Step B tert-butyl N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridii
  • reaction was stirred at 0°C for 30 mins followed by addition of iodomethane (3.399 mmol, 0.4825 g) (0.22 ml) and ⁇ , ⁇ -dimethylformamide (1 ml).
  • iodomethane 3.399 mmol, 0.4825 g
  • ⁇ , ⁇ -dimethylformamide 1 ml
  • the reaction mixture was allowed to warm to room temperature over 3 hours and then heated at 40°C for 15 min.
  • the reaction was neutralized with 2N HCI, diluted with 10 ml water, extracted with ethyl acetate (3X15 ml). Combined organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step C 5-ethvl-2-[3-ethvlsulfonvl-6-(methvlamino)-2-pvridvll-3-methvl-6-(trifluoromethyl)imidazo[4,5- c]pyridin-4-one A 2
  • Example P11 Preparation of 2-[5-[cvclopropyl(methyl)aminol-3-ethylsulfonyl-2-pyridyll-5-ethyl-3- methyl-6-(trifluoromethyl)imidazo[4,5-clpyridin-4-one A11.
  • Step B 2-[5-[cyclopropyl(methyl)amino]-3-ethylsulfonyl-2-pyridyl]-5-ethyl-3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one A11.
  • Example P12 Preparation of 2-[6-[cvclopropyl(methyl)aminol-3-ethylsulfonyl-2-pyridyll-5-ethyl-3- methyl-6-(trifluoromethyl)imidazo[4,5-clpyridin-4-one A12.
  • Example P13 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethvnimidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridvn-N-methyl-methanesulfonamide A13.
  • Step A N-[6-[5-ethvl-3-methvl-4-oxo-6-(trifluoromethvl)imidazo[4,5-clpvridin-2-vll-5-ethvlsulfonyl-3- pyridyl]-N-methylsulfonyl-methanesulfonanriide.
  • Step B N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2-yll-5-ethylsulfonyl-3- pyridyllmethanesulfonamide A15.
  • Step C N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3- pyridyl]-N-methyl-methanesulfonamide.
  • Example P14 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethvnimidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridyll-N-methyl-methanesulfonamide A14.
  • Example P15 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridyllmethanesulfonamide A15.
  • Example P16 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethvnimidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-2-pyridyllmethanesulfonamide A16.
  • Example P17 Preparation of N-cvclopropyl-6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethvnimidazo[4,5- cl pyrid in-2-yll-5-ethylsu Ifonyl-N-m ethyl-pyrid i ne-3-carboxam ide A17.
  • Step A 6-[5-ethvl-3-methvl-4-oxo-6-(trifluoromethvl)imidazo[4,5-clpvridin-2-vll-5-ethvlsulfonyl-pvridine- 3-carbonyl chloride.
  • Step B N-cyclopropyl-6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- ethylsulfonyl-N-methyl-pyridine-3-carboxamide A17.
  • Example P18 Preparation of N-cvclopropyl-6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5- cl pyrid in-2-yll-5-ethylsu Ifonyl-N-m ethyl-pyrid i ne-2-carboxam ide A18.
  • Example P19 Preparation of N-cvclopropyl-6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5- clpyridin-2-yll-5-ethylsulfonyl-pyridine-3-carboxamide A19.
  • Example P20 Preparation of N-cvclopropyl-6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5- cl pyrid in-2-yll-5-ethylsu Ifonyl-pyrid ine-2-carboxam ide A20.
  • Example P21 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethvnimidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridyll-N-methylsulfonyl-cyclopropanecarboxamide A21.
  • Example P22 Preparation of N'-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethvnimidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridyll-N,N'-dimethyl-cvclopropanecarbohydrazide A22.
  • Step A 2-[5-(2-benzhvdi lidenehvdrazino)-3-ethvlsulfonvl-2-pvridvll-5-ethvl-3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one
  • Step C 2-[5-[amino(methyl)amino]-3-ethylsulfonyl-2-pyridyl]-5-ethyl-3-methyl-6- (trifluoromethyl)imidazo[4,5-c]pyridin-4-one A56.
  • Step E N'-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3- pyridyl]-N,N'-dimethyl-cyclopropanecarbohydrazide.
  • reaction mixture was quenched with water and extracted with ethyl acetate.
  • the combined organic layers were washed with water, brine solution, dried with anhydrous sodium sulfate and concentrated under reduced pressure.
  • the residue was purified by column chromatography using ethyl acetate/cyclohexane to get the desired product N'-[6- [5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5-ethylsulfonyl-3-pyridyl]-N,N'- dimethyl-cyclopropane carbohydrazide (47 mg, 18%).
  • Example P23 Preparation of 6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2-yll-5- ethylsulfonyl-N-methylsulfonyl-pyridine-3-carboxamide A23.
  • Example P25 Preparation of N-(1-cvanocvclopropyl)-6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl) im idazo[4 , 5-cl pyrid in-2-yll-5-ethylsu Ifonyl-pyrid i ne-3-carboxam ide A25.
  • Example P27 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridyll-N'-methoxy-N-methyl-formamidine A27.
  • Example P28 Preparation of N-(cvanomethyl)-6-[5-ethyl-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-clpyridin-2-yll-5-ethylsulfonyl-pyridine-3-carboxamide A28.
  • Example P29 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-3-pyridyll-N-methylsulfonyl-methanesulfonamide A29.
  • Example P31 Preparation of 2-[5-chloro-6-(cvclopropylamino)-3-ethylsulfonyl-2-pyridyll-5-ethyl-3- methyl-6-(trifluoromethyl)imidazo[4,5-clpyridin-4-one A31.
  • the mixture was cooled to RT, quenched with a saturated solution of Sodium bicarbonate.
  • the aqueous phase was extracted three times with DCM, washed with aqueous Sodium bicarbonate, dried with sodium sulfate, filtered, and 2g Isolute was added.
  • the residu was purified by chromatography with DCM: EA 0-40% over 12g silica gel to give the tittle compound (79.8 mg, 24% yield) and the starting material (183.2 mg).
  • Example P32 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-2-pyridyll-N-(2,2,2-trifluoroethyl)cyclopropanecarboxamide A32.
  • Example P33 Preparation of N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-clpyridin-2- yll-5-ethylsulfonyl-2-pyridyll-N-(2,2,2-trifluoroethyl)cyclopropanecarboxamide A33.
  • reaction was stirred at 0°C for 30 mins, to this was added iodomethane (0.2542 mmol, 0.03608 g), and reaction was stirred at room temperature for 2 hours. After this TLC was checked, LCMS shows product mass, reaction went to completion.
  • reaction was quenched in 10 ml of water extracted with ethyl acetate. Combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure.
  • Example P34 Preparation of 5-ethyl-2-[3-ethylsulfonyl-6-(2,2,2-trifluoroethylamino)-2-pyridyll-3- methyl-6-(trifluoromethyl)imidazo[4,5-clpyridin-4-one A34.
  • Example P35 Preparation of N-cvclopropylsulfonyl-6-[5-ethyl-3-methyl-4-oxo-6- (trifluoromethyl)imidazo[4,5-clpyridin-2-yll-5-ethylsulfonyl-pyridine-3-carboxamide A35.
  • Example P37 N-[6-[5-ethyl-3-methyl-4-oxo-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]-5- ethylsulfonyl-3-pyridyl]-N-methyl-cyclopropanesulfonamide A37

Abstract

L'invention concerne des composés de formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1, et les sels, stéréoisomères, énantiomères, tautomères et N-oxydes, acceptables au plan agrochimique, de ces composés, qui peuvent être utilisés en tant qu'insecticides, et préparés de manière connue.
EP16790995.1A 2015-11-16 2016-11-03 Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre Active EP3377489B1 (fr)

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CN109890818B (zh) * 2016-10-27 2022-11-25 先正达参股股份有限公司 具有硫和羟胺取代基的杀有害生物活性杂环衍生物
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WO2019053182A1 (fr) 2017-09-18 2019-03-21 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre
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JP2022549417A (ja) 2019-09-20 2022-11-25 シンジェンタ クロップ プロテクション アクチェンゲゼルシャフト 硫黄及びスルホキシミン含有置換基を有する殺有害生物的に活性な複素環式誘導体
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TW202134214A (zh) * 2020-03-04 2021-09-16 瑞士商先正達農作物保護公司 用於製備具有3-含硫取代基的5-氯-吡啶-2-甲酸醯胺以及甲酸鹽之方法
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US20180354942A1 (en) 2018-12-13
JP2019503342A (ja) 2019-02-07
BR112018009852A2 (pt) 2018-11-13
EP3377489B1 (fr) 2020-10-07

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